1-(dichloro-4&#39;-sulfamoyl or substituted sulfamoyl-phenyazo)-2-hydroxy-3-phenylcarbamoyl or substituted phenylcarbamoyl-naphthalenes

ABSTRACT

##STR1## wherein each R 1  is independently hydrogen, C 1-8  alkyl, cyclohexyl or C 2-3  alkyl substituted by 1 or 2 substituents selected from halo, hydroxy, cyano, methoxy, ethoxy and (C 1-2  alkoxy)-carbonyl, and 
     each of R 2  and R 3  is independently hydrogen, chloro, bromo, methyl, methoxy or ethoxy, 
     useful as pigments for, for example, the mass pigmenting of viscose and surface coatings such as oil and water base paints, lacquers and inks, pigment printing, textile coating and pigmenting paper in the mass.

This is a continuation of application Ser. No. 06/812,871, filed Dec. 23, 1985 and now abandoned, which is a division of application Ser. No. 06/659,246, filed Oct. 10, 1984 and now U.S. Pat. No. 4,623,397, which, in turn, is a division of application Ser. No. 06/410,175, filed Aug. 20, 1982 and now abandoned.

The invention relates to azo compounds.

The invention provides azo compounds of formula I ##STR2## in which each R₁, independently, is hydrogen; C₁₋₈ alkyl; C₂₋₃ alkyl substituted by up to two substituents selected from halogen, hydroxy, cyano, methoxy, ethoxy and (C₂₋₂ alkoxy) carbonyl; or cyclohexyl,

and each of R₂ and R₃, independently, is hydrogen, chlorine, bromine, methyl, methoxy or ethoxy.

Any unsubstituted alkyl group as R₁ may be straight-chain or branched. The substituted C₁₋₈ alkyl groups are preferably C₁₋₄ alkyl, more preferably C₁₋₃ alkyl and particularly methyl or ethyl groups.

Halogen is preferably chlorine or bromine, more preferably chlorine.

Preferably the substituted C₂₋₃ alkyl groups as R₁ are mono-substituted. Preferred substituents are cyano, hydroxy, methoxy, ethoxy and chlorine, more preferably hydroxy.

Each R₁ is preferably R₁ ', where either both R₁ ' are identical and signify C₁₋₂ alkyl or one R₁ ' is hydrogen and the other is C₁₋₂ alkyl.

R₂ is preferably R₂ ', where R₂ ' is hydrogen, chlorine, methyl, methoxy or ethoxy. More preferably, R₂ is R₂ ", where R₂ " is methyl or methoxy.

R₃ is preferably R₃ ', where R₃ ' is hydrogen, chlorine or methyl. More preferably, R₃ is hydrogen.

Preferred compounds of formula I are those in which each R₁ is R₁ ', R₂ is R₂ ' and R₃ is R₃ '. More preferred compounds of formula I are thos in which R₂ is R₂ " and R₃ is hydrogen.

The present invention further provides a process for the production of azo compounds of formula I comprising coupling a diazo derivative of an amine of formula II ##STR3## with a compound of formula III ##STR4##

The diazotization and coupling reactions are carried out in accordance with known methods.

The compounds of formulae II and III are either known or may be prepared in accordance with known methods from available starting materials.

The resulting compounds of formula I may be isolated and purified in conventional manner.

The compounds of formula I are useful as pigments, e.g. for the mass pigmenting of, e.g., viscose, surface coatings such as paints, whether of an oil or water base, lacquers and inks. They may also be used in pigment printing, textile coating and for pigmenting paper in the mass. They may be employed for such uses in conventional manner and in conventional amounts.

The pigmentations obtained employing the compounds of formula I possess notably good fastness properties.

Before use, i.e. after synthesis, the pigments of formula I may be post-treated in an organic solvent, e.g. treated at the boil for a period up to 24 hours in a solvent such as ethanol, 2-methoxyethanol, 2-ethoxyethanol, o-dichlorobenzene or dimethylformamide and preferably milled. Such a treatment may be desirable since it may allow the conversion of the pigment into another advantageous crystalline form or have a purifying effect.

The following Examples, in which all parts and percentages are by weight and all temperatures in degrees Centigrade, illustrate the invention.

EXAMPLE 1

(a) Diazotization

53.8 Parts 1-amino-2,5-dichlorobenzene-4-sulphonic acid dimethylamide are slowly introduced with stirring into a mixture of 147 parts glacial acetic acid and 60 parts water. After the mixture has been stirred at room temperature for 16 hours, 117 parts 30% hydrochloric acid are added, the mixture is then cooled to about 0° C. by the addition of 60 parts ice and simultaneously 14 parts of a 4N sodium nitrite solution are added over the course of 5 minutes. The resulting mixture is then stirred for 1 hour at 0°-5° and thereafter the excess sodium nitrite is destroyed with a small amount of aminosulphonic acid. After 5 minutes stirring, 2.0 parts filtering earth are added to the mixture which is then filtered. The filtration residue is washed with 10 parts water which are then combined with the filtrate.

(b) Coupling component

58.6 Parts 2-hydroxy-3-naphthoic acid-2'-methoxyphenylamide are dissolved with stirring in 350 parts water, 10 parts commercially available anionic surfactant (liquid) and 53.4 parts NaOH 30%. 2.0 Parts filtering earth are added and the mixture is subsequently filtered. The filtration residue is washed with 10 parts water which are then combined with the filtrate.

(c) Coupling

10 Parts commercially available anionic surfactant in liquid form are added to the diazonium salt solution (a) above and the resulting mixture is cooled to 0°-5°. Whilst cooling and stirring, the coupling component solution prepared under b) is added to the mixture over 3 hours. The reaction mixture is further stirred for 2 hours at 0°-5° and then for 1 hour at 22°-25°, heated for 1 hour at 80° and finally filtered. The resulting pigment is washed with 5,000 parts water and then dried. The product possesses a scarlet shade.

By treating the pigment for about 2 hours in dimethylformamide at the boil, there is obtained a product having a red shade; when used after milling for colouring surface coatings, the resulting pigmentations have good light fastness.

EXAMPLE 2

12.75 Grams 1-amino-2,5-dichlorobenzene-4-sulphonic acid mono-methylamide are introduced with stirring into 50 ml glacial acetic acid and 20 ml 30% hydrochloric acid. After the mixture has been cooled to about 0°, 6.3 ml of a 8N sodium nitrite solution are slowly added with stirring and stirring is then continued at 0°-5° for a further hour. The excess nitrite is destroyed by the addition of a small amount of aminosulphonic acid and the diazonium salt solution is filtered.

13.85 Grams 2-hydroxy-3-naphthoic acid (2'-methylphenyl)amide are dissolved in 62 ml water and 10 ml 30% NaOH. After the addition of 2.5 ml commercially available liquid anionic surfactant, the mixture is cooled to about 0° and then added very slowly with stirring to the cooled diazonium solution. Stirring is then continued for a further hour at about 0°, 4 hours at 20° and 1 hour at 90°. The resulting red pigment is filtered, washed acid-free and dried in conventional manner.

EXAMPLE 3

By following the procedure of Example 1, 1-amino-2,5-dichlorobenzene-4-sulphonic acid dimethylamide is diazotised and coupled with 2-hydroxy-3-naphthoic acid-4'-chlorophenylamide. The resulting pigment is treated at reflux for 1 hour in dimethylformamide and milled. This treatment produces a shade change from red to orange. The light fastness of the resulting pigmentations are improved.

By following the procedure of Examples 1, 2 and 3, the compounds of the formula ##STR5## as defined in Table 1 are obtained.

                  TABLE 1                                                          ______________________________________                                                                            Posi-                                                                          tion of                                     Ex.                                the 2nd                                     No.  R.sub.1 R'.sub.1                                                                               R.sub.2                                                                               R.sub.3                                                                               Cl    Shade                                 ______________________________________                                          4   --CH.sub.3                                                                             --CH.sub.3                                                                             H      H      5     yellowish-                                                                     red                                    5   "       "       2-CH.sub.3                                                                            H      5     red                                    6   "       "       2-OCH.sub.3                                                                           4-OCH.sub.3                                                                           5     red                                    7   "       "       4-Cl   H      5     red                                    8   "       "       4-Cl   H      5     yellowish-                                                                     red                                    9   "       "       2-CH.sub.3                                                                            4-Cl   5     yellowish-                                                                     red                                   10   "       "       2-Cl   4-Cl   5     yellowish-                                                                     red                                   11   "       "       2-Cl   5-Cl   5     red                                   12   "       "       2-Cl   H      5     red                                   13   "       "       4-OCH.sub.3                                                                           H      5     yellowish-                                                                     red                                   14   "       "       4-Cl   H      6     yellowish-                                                                     red                                   15   "       "       2-OC.sub.2 H.sub.5                                                                    H      5     yellowish-                                                                     red                                   16   "       H       2-OCH.sub.3                                                                           H      5     red                                   17   --C.sub.2 H.sub.5                                                                      --C.sub.2 H.sub.5                                                                      "      H      5     red                                   18   H       H       2-CH.sub.3                                                                            H      5     red                                   19   H       H       2-CH.sub.3                                                                            4-Cl   5     red                                   20   --CH.sub.3                                                                             H       "      H      5     red                                   21   "       H       "      4-Cl   5     red                                   22   --C.sub.2 H.sub.5                                                                      H       "      H      5     red                                   23   "       H       "      4-Cl   5     red                                   24   --CH.sub.3                                                                             H       H      H      5     red                                   25   --C.sub.2 H.sub.5                                                                      H       H      H      5     red                                   26   "       H       2-OCH.sub.3                                                                           H      5     red                                   27   --C.sub.2 H.sub.5                                                                      --C.sub.2 H.sub.5                                                                      H      H      5     yellowish-                                                                     red                                   ______________________________________                                    

By following the procedure of Examples 1, 2 and 3, the compounds of the formula ##STR6## as defined in Table 2 are obtained.

    __________________________________________________________________________     Ex.                       Position of                                          No.                                                                               R.sub.1 R.sub.1 ' R.sub.2                                                                             the 2nd chlorine                                                                       Shade                                        __________________________________________________________________________     28 CH.sub.2 CH.sub.2 CN                                                                   CH.sub.2 CH.sub.2 CN                                                                     2-CH.sub.3                                                                          5       red                                          29 "       "         2-OCH.sub.3                                                                         5       red                                          30 H       "         2-CH.sub.3                                                                          5       red                                          31 H       CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                     2-CH.sub.3                                                                          5       red                                          32 CH.sub.2 CH.sub.2 OH                                                                   CH.sub.2 CH.sub.2 OH                                                                     2-CH.sub.3                                                                          5       red                                          33 "       "         2-OCH.sub.3                                                                         5       red                                          34 H       "         2-CH.sub.3                                                                          5       red                                          35 H       "         2-OCH.sub.3                                                                         5       red                                          36 CH.sub.2 CH.sub.2 OCH.sub.3                                                            CH.sub.2 CH.sub.2 OCH.sub.3                                                              2-CH.sub.3                                                                          5       red                                          37 H       "         2-OCH.sub.3                                                                         5       red                                          38                                                                                 ##STR7##                                                                              H         2-CH.sub.3                                                                          5       red                                          39 "                                                                                       ##STR8## 2-CH.sub.3                                                                          5       red                                          40 CH.sub.2 CH.sub.2 Cl                                                                   H         2-CH.sub.3                                                                          6       red                                          41 CH.sub.2 CH.sub.2 CH.sub.3                                                             CH.sub.2 CH.sub.2 CH.sub.3                                                               2-CH.sub.3                                                                          6       red                                          42 H       "         2-CH.sub.3                                                                          6       red                                          43 H       CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                      2-OCH.sub.3                                                                         6       red                                          __________________________________________________________________________

The compounds of Examples 4 to 6 and 8 to 14 are preferably aftertreated in boiling dimethylformamide and milled.

APPLICATION EXAMPLE

Four parts of the pigment of Example 1 are added to 96 parts of a mixture of

50 parts of a 60% solution of coco aldehyde-melamine resin of 32% fat content in xylene,

30 parts of a 50% melamine resin solution in butanol,

10 parts of xylene and

10 parts of ethylene glycol monoethylether

and the mixture ground for 24 hoours in a ball mill. The dispersion obtained is sprayed on an aluminum sheet, and the spray coating is allowed to dry in the air for 30 minutes and then stoved for 30 minutes at 120°. A scarlet film with very good light and weathering fastness is obtained. 

What is claimed is:
 1. A compound of the formula ##STR9## wherein each R₁ is independently hydrogen, C₁₋₈ alkyl, cyclohexyl or C₂₋₃ alkyl substituted by 1 or 2 substituents selected from halo, hydroxy, cyano, methoxy, ethoxy and (C₁₋₂ alkoxy)-carbonyl, andeach of R₂ and R₃ is independently hydrogen, chloro, bromo, methyl, methoxy or ethoxy.
 2. A compound according to claim 1 wherein R₂ is hydrogen, chloro, methyl, methoxy, or ethoxy.
 3. A compound according to claim 1 wherein R₂ is methyl or methoxy.
 4. A compound according to claim 1 wherein R₃ is hydrogen, chloro or methyl.
 5. A compound according to claim 4 wherein R₃ is hydrogen.
 6. A compound according to claim 1wherein both R₁ 's are identical and are C₁₋₂ alkyl or one R₁ is hydrogen and the other is C₁₋₂ alkyl.
 7. A compound according to claim 6wherein R₂ is hydrogen, chloro, methyl, methoxy or ethoxy, and R₃ is hydrogen, chloro or methyl.
 8. A compound according to claim 7wherein R₂ is methyl or methoxy, and R₃ is hydrogen.
 9. A compound according to claim 7 having the formula ##STR10## wherein both R₁ ''s are identical and are C₁₋₂ alkyl or one R₁ ' is hydrogen and the other is C₁₋₂ alkyl,R₂ ' is hydrogen, chloro, methyl, methoxy or ethoxy, and R₃ ' is hydrogen, chloro or methyl.
 10. A compound according to claim 9wherein R₂ ' is methyl or methoxy, and R₃ ' is hydrogen.
 11. The compound according to claim 10 having the formula ##STR11##
 12. The compound according to claim 10 having the formula ##STR12##
 13. The compound according to claim 9 having the formula ##STR13##
 14. The compound according to claim 9 having the formula ##STR14##
 15. The compound according to claim 9 having the formula ##STR15##
 16. The compound according to claim 9 having the formula ##STR16##
 17. The compound according to claim 10 having the formula ##STR17##
 18. The compound according to claim 10 having the formula ##STR18##
 19. The compound according to claim 5 having the formula ##STR19## 